Fluorine-modified comb polymers based on acryloydimethyltaurine acid

ABSTRACT

The invention provides water-soluble or water-swellable copolymers obtained by free-radical copolymerization of 
     A) acryloyldimethyltaurine and/or acryloyldimethyltaurates, 
     B) optionally, one or more other olefinically unsaturated, optionally crosslinking, comonomers containing at least one oxygen, nitrogen, sulfur or phosphorus atom and possessing a molecular weight of less than 500 g/mol, and 
     C) one or more at least monofunctional, fluorine-containing components capable of free-radical polymerization, the copolymerization 
     D) taking place in the presence or absence of at least one polymeric additive having number-average molecular weights of from 200 g/mol to 10 9  g/mol. 
     The water-soluble or water-swellable copolymers of the present invention are useful in paper processing, laundry detergents, textile processing, petroleum extraction and formulating cosmetics.

The present invention relates to fluorine-modified comb polymers basedon acryloyldimethyltaurine.

In recent years water-soluble polymers have acquired a continuallyincreasing importance in industry and science. In volume terms,polyelectrolytes are occupying a very large proportion of the overallannual production. They find application, for example, in paperprocessing, in the laundry detergents industry, in textile processing,in petroleum extraction or as important base materials for cosmetics. Inthe cosmetics sector a supporting role is played by polyelectrolytes.Besides water-soluble surface-active substances there is a high demandin this sector for systems which thicken oil and water. Thickeners ofthis kind, particularly the “superabsorbents” prepared on the basis ofpolyacrylic acid, have progressed since their development in the 1970sto become a pillar of the hygiene sector. In their crosslinked versions,partly or fully neutralized polyacrylic acids and their water-solublecopolymers are employed in numerous cosmetic formulations as bodyingagents. The diversity of possible structures and the diverse possibleapplications associated therewith are manifested not least in a host ofpatents filed worldwide since the mid-1970s. In the 1990s, innovativethickeners based on 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS)and their salts were introduced into the market (EP 816 403 and WO98/00094). In both homopolymer and copolymer form (®Aristoflex AVC,Clariant GmbH) such thickeners are superior in many respects to thecorresponding polycarboxylates (Carbopols). For example, thickenersystems based on AMPS display outstanding properties in pH ranges belowpH 6, i.e., in a pH range in which it is no longer possible to operatewith conventional polycarboxylate thickeners. Moreover, the microgelstructure of such thickeners leads to a particularly pleasant skinsensation. The ease of processing and the favorable toxicologicalprofile of the principal monomer imbue these thickeners with a highapplication potential.

Over recent years representatives of a new thickener design have enteredthe market. In these thickeners two different properties have beencombined in one polymer, thereby opening up new fields of application.Thickening emulsifiers or dispersants are but two examples of this newclass of substance. Brand names that may be mentioned include thePemulens® TR-1 and TR-2 from BF Goodrich or the Aculyn® products fromRohm & Haas. All existing versions are based on hydrophobically modifiedversions of the conventional polyacrylates.

Comparable polymers which develop hydrophobic interactions and hencephysical crosslinking through fluorine-containing groups were hithertounknown. Some fluorotelomers which possess one or a maximum of twofluorine-containing groups per polymer chain are available.

Through free-radical copolymerization of acryloyldimethyltaurine (AMPS)and/or its salts with suitable vinylically monofunctional orpolyfunctional fluorine derivatives, in the presence where appropriateof comonomers and polymeric additives, it was possible to synthesizeboth crosslinked and noncrosslinked structures having highlyadvantageous performance properties.

The invention provides water-soluble or water-swellable copolymerspreparable by free-radical copolymerization of:

A) acryloyldimethyltaurine and/or acryloyldimethyltaurates,

B) if desired, one or more other olefinically unsaturated, optionallycrosslinking, comonomers containing at least one oxygen, nitrogen,sulfur or phosphorus atom and possessing a molecular weight of less than500 g/mol, and

C) one or more at least monofunctional, fluorine-containing componentscapable of free-radical polymerization, the copolymerization

D) taking place in the presence or absence of at least one polymericadditive having number-average molecular weights of from 200 g/mol to10⁹ g/mol.

The copolymers of the invention preferably possess a molecular weight offrom 10³ g/mol to 10⁹ g/mol, more preferably from 10⁴ to 10⁷ g/mol, verypreferably from 5*10⁴ to 5*10⁶ g/mol.

The acryloyldimethyltaurates can be the organic or inorganic salts ofacryloyl-dimethyltaurine. Preference is given to the Li⁺, Na⁺, K⁺, Mg⁺⁺,Ca⁺⁺, All⁺⁺⁺ and/or NH₄ ⁺ salts. Likewise preferred are themonoalkylammonium, dialkylammonium, trialkylammonium and/ortetraalkylammonium salts, in which the alkyl substituents of the aminesmay independently of one another be (C₁-C₂₂)-alkyl radicals or(C₂-C₁₀)-hydroxyalkyl radicals. Preference is also given to mono- totriethoxylated ammonium compounds with a different degree ofethoxylation. It should be noted that the invention also embracesmixtures of two or more of the abovementioned representatives.

The degree of neutralization of the acryloyldimethyltaurine can bebetween 0 and 100%, particular preference being given to a degree ofneutralization of more than 80%.

Based on the total mass of the copolymers, the amount ofacryloyldimethyltaurine and/or acryloyldimethyltaurates is at least 0.1%by weight, preferably from 20 to 99.5% by weight, more preferably from50 to 98% by weight.

As comonomers B) it is possible to use all olefinically unsaturatedmonomers whose reaction parameters allow copolymerization withacryloyldimethyltaurine and/or acryloyldimethyltaurates in therespective reaction media. Preferred comonomers B) are unsaturatedcarboxylic acids and their anhydrides and salts, and also their esterswith aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromaticalcohols having a carbon number of from 1 to 22. Particularly preferredunsaturated carboxylic acids are acrylic acid, methacrylic acid,styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconicacid, and senecic acid. Preferred counterions are Li⁺, Na⁺, K⁺, Mg⁺⁺,Ca⁺⁺, Al⁺⁺⁺, NH₄ ⁺, monoalkylammonium, dialkylammonium, trialkylammoniumand/or tetraalkylammonium radicals, in which the alkyl substituents ofthe amines independently of one another are (C₁-C₂₂)-alkyl radicals or(C₂-C₁₀)-hydroxyalkyl radicals. It is additionally possible to employmono- to triethoxylated ammonium compounds with a different degree ofethoxylation. The degree of neutralization of the carboxylic acids canbe between 0 and 100%. Further preferred comonomers are open-chainN-vinyl amides, preferably N-vinylformamide (VIFA),N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) andN-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams) with a ringsize of 3 to 9, preferably N-vinylpyrrolidone (NVP) andN-vinylcaprolactam; amides of acrylic and methacrylic acid, preferablyacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, and N,N-diisopropylacrylamide; alkoxylatedacrylamides and methacrylamides, preferably hydroxyethyl methacrylate,hydroxymethylmethacrylamide; hydroxyethylmethacrylamide,hydroxypropylmethacrylamide, and mono[2-(methacryloyloxy)ethyl]succinate; N,N-dimethylamino methacrylate; diethylaminomethylmethacrylate; acrylamido- and methacrylamidoglycolic acid; 2- and4-vinylpyridine; vinyl acetate; glycidyl methacrylate; styrene;acrylonitrile; vinyl chloride; stearyl acrylate; lauryl methacrylate;vinylidene chloride; and/or tetrafluoroethylene. Likewise suitablecomonomers B) are inorganic acids and their salts and esters. Preferredacids are vinylphosphonic acid, vinylsulfonic acid, allylphosphonicacid, and methallylsulfonic acid.

The weight fraction of the comonomers B), based on the total mass of thecopolymers, can be from 0 to 99.8% by weight and is preferably from 0.5to 80% by weight, more preferably from 2 to 50% by weight.

Suitable polymerizable fluorine-containing components C) include allcompounds which are olefinically at least monounsaturated and which arecapable of free-radical copolymerization with acryloyldimethyltaurineand/or acryloyldimethyl-taurates—and optionally further comonomers—underthe reaction conditions chosen in each case. The distribution of theindividual fluorine-containing monomers across the polymer chains whichform need not necessarily be random. The invention also embraces theformation of blocklike (including multiblock) or gradientlikestructures, for example. Combinations of two or more differentfluorine-containing components C) are also possible, it being clear tothe expert that monofunctional representatives lead to the formation ofcomb-shaped structures while di-, tri-, or polyfunctional components C)lead to structures which are at least partly crosslinked.

Preferred fluorine-containing components C) are those of formula (I).

R¹—Y—(CH₂)_(r)(CF₂)_(s)CF₃  (I)

In this formula R¹ represents a polymerizable function from the group ofthe vinylically unsaturated compounds which is suitable for theconstruction of polymeric structures by a free-radical route. R¹ ispreferably a vinyl, allyl, methallyl, methylvinyl, acryloyl(CH₂═CH—CO—), methacryloyl (CH₂═C[CH₃]—CO—), crotonyl, senecionyl,itaconyl, maleyl, fumaryl or styryl radical, more preferably an acryloylor methacryloyl radical. The attachment of the fluorine-containing groupto the reactive end group R¹ requires a suitable chemical bridge Y.Preferred bridges Y are —O—, —C(O)—, —C(O)—O—, —S—, —O—CH₂—CH(O—)—CH₂OH,—O—CH₂—CH(OH)—CH₂—O—, —O—SO₂—O—, —O—S(O)—O—, —PH—, —P(CH₃)—, —PO₃—,—NH—, —N(CH₃)—, —(C₁ to C₅₀)alkyl-O—, -phenyl-O—, -benzyl-O—, —(C₅ toC₈)cycloalkyl-O—, —(C₁-C₅₀)alkenyl-O—, —(CH(CH₃)—CH₂—O)_(n)—,—O—(CH₂—CH₂—O)_(n)—, and —([CH(CH₃)—CH₂—O]_(n)—[CH₂—CH₂—O]_(m)) _(o)—,where n, m, and o independently of one another denote numbers from 0 to200 and the distribution of the EO and PO units can be random or in theform of blocks. r and s are stoichiometric coefficients whichindependently of one another can be numbers between 0 and 200.

Particularly preferred fluorine-containing components C) are

perfluorohexylethanol methacrylate,

perfluorohexoylpropanol methacrylate,

perfluoroctylethanol methacrylate,

perfluoroctylpropanol methacrylate,

perfluorohexylethanolyl polyglycol ether methacrylate,

perfluorohexoylpropanolyl poly[ethylglycol-co-propylene glycol ether]acrylate, perfluoroctylethanolyl poly[ethylglycol-block-co-propyleneglycol ether] methacrylate

and/or perfluoroctylpropanolyl polypropylene glycol ether methacrylate.

Based on the total mass of the copolymers the weight fraction of thecomonomers C) can be from 0.1 to 99.9% by weight, preferably from 0.1 to50% by weight, more preferably from 0.2 to 30% by weight, and verypreferably from 0.5 to 20% by weight.

In one preferred embodiment the copolymerization is conducted in thepresence of at least one polymeric additive D), the additive D) beingadded wholly or partly in solution to the polymerization medium beforethe actual copolymerization. The use of two or more additives D) islikewise in accordance with the invention. Crosslinked additives D) maylikewise be used. The additives D) or mixtures thereof must only bewholly or partly soluble in the chosen polymerization medium. During theactual polymerization step the additive D) has a number of functions. Onthe one hand it prevents the formation of overcrosslinked polymerfractions in the copolymer which forms in the actual polymerizationstep, and on the other hand the additive D) is statistically attacked byactive free radicals in accordance with the very well-known mechanism ofgraft copolymerization. Depending on the particular additive D), thisresults in greater or lesser fractions of the additive beingincorporated into the copolymers. Moreover, suitable additives D)possess the property of altering the solution parameters of thecopolymers which form during the free-radical polymerization reaction insuch a way that the average molecular weights are shifted to highervalues. As compared with analogous copolymers prepared without theaddition of the additives D), those prepared with the addition ofadditives D) advantageously exhibit a significantly higher viscosity inaqueous solution.

Preferred additives D) are homopolymers and copolymers which are solublein water and/or alcohols. The term “copolymers” also comprehends thosehaving more than two different monomer types. Particularly preferredadditives D) are homopolymers and copolymers of N-vinylformamide,N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide, propylene oxide,acryloyldimethyltaurine, N-vinylcaprolactone, N-vinylmethylacetamide,acrylamide, acrylic acid, methacrylic acid, N-vinylmorpholide,hydroxyethyl methacrylate, diallyidimethylammonium chloride (DADMAC)and/or [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC);polyalkylene glycols and/or alkylpolyglycols.

Particularly preferred additives D) are polyvinylpyrrolidones (e.g.,K15®, K20® and K30® from BASF), poly(N-vinylformamides),poly(N-vinylcaprolactams), and copolymers of N-vinylpyrrolidone,N-vinylformamide and/or acrylic acid, which may also have been partly orfully hydrolyzed.

The molecular weight of the additives D) is preferably from 10² to 10⁷g/mol, more preferably from 0.5*10⁴ to 10⁶ g/mol.

The amount in which the polymeric additive D) is used, based on thetotal mass of the monomers to be polymerized during thecopolymerization, is preferably from 0.1 to 90% by weight, morepreferably from 1 to 20% by weight, and with particular preference from1.5 to 10% by weight.

In one further preferred embodiment the copolymers of the invention arecrosslinked, i.e., they contain comonomers containing at least twopolymerizable vinyl groups. Preferred crosslinkers aremethylenebisacrylamide; methylenebismethacrylamide; esters ofunsaturated monocarboxylic and polycarboxylic acids with polyols,preferably di-acrylates and tri-acrylates and -methacrylates, morepreferably butanediol and ethylene glycol diacrylate and -methacrylate,trimethylolpropane triacrylate (TMPTA) and trimethylolpropanetrimethacrylate (TMPTMA); allyl compounds, preferably allyl(meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters,tetraallyloxyethane, triallylamine, tetraallylethylenediamine; allylesters of phosphoric acid; and/or vinylphosphonic acid derivatives.

A particularly preferred crosslinker is trimethylolpropane triacrylate(TMPTA).

The weight fraction of crosslinking comonomers, based on the total massof the copolymers, is preferably up to 20% by weight, more preferablyfrom 0.05 to 10% by weight, and very preferably from 0.1 to 7% byweight.

The polymerization medium used may comprise all organic or inorganicsolvents which have a very substantially inert behavior with respect tofree-radical polymerization reactions and which advantageously allow theformation of medium or high molecular weights. Those used preferablyinclude water; lower alcohols; preferably methanol, ethanol, propanols,iso-, sec- and t-butanol, very preferably t-butanol; hydrocarbons having1 to 30 carbon atoms, and mixtures and emulsions of the aforementionedcompounds.

The polymerization reaction takes place preferably in the temperaturerange between 0 and 150° C., more preferably between 10 and 100° C.,either at atmospheric pressure or under elevated or reduced pressure. Ifdesired the polymerization may also be performed under an inert gasatmosphere, preferably under nitrogen.

In order to initiate the polymerization it is possible to usehigh-energy electromagnetic rays, mechanical energy, or the customarychemical polymerization initiators, such as organic peroxides, e.g.,benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketoneperoxide, cumene hydroperoxide, dilauroyl peroxide (DLP) or azoinitiators, such as azodiisobutyronitrile (AIBN) and azobisamidopropylhydrochloride (ABAH), for example. Likewise suitable are inorganicperoxy compounds, such as (NH₄)₂S₂O₈, K₂S₂O₈ or H₂O₂, for example, whereappropriate in combination with reducing agents (e.g., sodiumhydrogensulfite, ascorbic acid, iron(II) sulfate, etc.) or redox systemscomprising as reducing component an aliphatic or aromatic sulfonic acid(e.g., benzenesulfonic acid, toluenesulfonic acid, etc.).

The polymerization reaction is advantageously conducted, for example, asa precipitation polymerization, emulsion polymerization, solutionpolymerization, bulk polymerization, or gel polymerization. Particularlyadvantageous for the profile of properties of the copolymers of theinvention is precipitation polymerization, preferably in tert-butanol.The copolymers of the invention are very suitable for stabilizing andthickening fluorine-containing aqueous systems. By fluorine-containingaqueous systems are meant for example mixtures of water withfluoroalcohols, fluorosurfactants or fluoroalkanes. A particularpossibility is that of stabilizing fluorine-containing emulsions withvery high fractions of fluoroalkyl compounds, perfluoroalkylethanols,perfluoroalkylpropanols, and fluorosurfactants (>30%). The copolymersare also extremely suitable for stabilizing combination formulations,containing for example fats or oils, including silicone oils, incombination with fluorine-containing compounds. In the case of thecopolymers the fluorine content can be varied virtually as desired,resulting in a broad property spectrum. A further advantage of thecopolymers is that the aggregation-capable hydrophobicfluorine-containing group is at the same time also lipophobic, resultingin the attractive hydrophobic interactions occurring exclusively betweenthe fluorine-containing groups. As a consequence, in an aqueous solutionor a hydrogel, for example, lipophilic groups or molecules do not enterinto interaction with the fluorine-containing groups of the polymers.Accordingly, in a system containing water and oil, for example, it ispossible to influence specifically the consistency of the aqueous phasewithout affecting the viscosity of the oil phase. This is of advantageif, for example, a phase separation is desired. Also conceivable,therefore, are applications in electrical engineering orelectrophoresis. The polymers of the invention may likewise be used tomediate attractive interactions between fluorinated surfaces andhydrophilic boundary media. This property is of interest, for example,for the construction of selective membranes. It is likewise possible toeffect compatibilization, dispersion or wetting of fluorine-containingpolymers or polymer particles. Hydrophilic surfaces, such as ceramic,minerals, glass, metal or else fabrics and leather, can behydrophobized, for example, by the polymers of the invention. In thecosmetics sector the copolymers can be used, for example, to formulate avery wide variety of W/O emulsions and O/W emulsions. Examples are skinprotection formulations, shampoos, rinses, lotions, treatments,decorative cosmetics, makeup, powders, deosticks, antiperspirants,shower baths, liquid soap, bar soap, cleansing milk, sun protectionformulations, hair colorants, hair gels, and hair sprays, to name but afew. An advantageous feature in the case of cosmetic applications isthat the copolymers impart a pleasant skin feel to the compositions. Inthe case of applications in the hair cosmetology sector the copolymersexhibit a pleasant conditioning effect of the polymers and give the hairgood combability and shine.

The following examples are intended to illustrate the invention without,however, restricting it thereto.

EXAMPLE 1

Reactants amount (g) NH₃-neutralized AMPS 80 ® Perfluoroctylpropylolmethacrylate 10 t-Butanol 400 DLP (initiator) 1 Poly-N-vinylpyrrolidone(® K-15BASF) 5

The polymer was prepared by the precipitation method in tert-butanol.The reactants in t-butanol were introduced as an initial charge and thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of dilauroyl peroxide (DLP). Thepolymer was isolated by removal of the solvent under suction and bysubsequent vacuum drying. In 1% aqueous solution the polymer exhibits aviscosity of 45 000 mPas, with a slightly opalescent appearance. Theskin feel of the gel was markedly superior to that of fluorine-freeversions.

EXAMPLE 2

Reactants amount (g) NH₃-neutralized AMPS 70 N-Vinylpyrrolidone 5Perfluoroctylethyloxyglyceryl methacrylate 8 Isopropanol 500 AIBN(initiator) 1

The polymer was prepared by the solution polymerization method inisopropanol. The monomers were dissolved in the corresponding alcohol,the reaction mixture was rendered inert, and then, after initialheating, the reaction was initiated by addition of diazoisobutyronitrile(AIBN). The polymer solution was subsequently concentrated and thepolymer was isolated by vacuum drying.

EXAMPLE 3

Reactants amount (g) AMPS 80 Perfluoroctylpolyethylene glycolmethacrylate 20 Cyclohexane 200 Water 300 ® Span 80 1 Na₂S₂O₈(initiator) 1

The polymer was prepared by the emulsion method in water. The monomerswere emulsified in a water/cyclohexane mixture using ®Span 80, thereaction mixture was rendered inert using N₂, and then, after initialheating, the reaction was initiated by addition of sodiumperoxodisulfate. The polymer emulsion was subsequently evaporated down(cyclohexane acting as azeotrope former for water) and by this means thepolymer was isolated.

EXAMPLE 4

Reactants amount (g) NH₃-neutralized AMPS 80 Perfluorohexylpolyethyleneglycol methacrylate 20 t-Butanol 300 DLP (initiator) 1

This polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of (dilauroyl peroxide) DLP. Thepolymer was isolated by removal of the solvent under suction andsubsequent vacuum drying. In 1% solution in distilled water the polymerexhibits a clear appearance with a viscosity of 35 000 mPas. Incomparison therewith the fluorine-free version, with the samecomposition, showed a similar appearance and a viscosity of 12 000 mPasunder identical measurement conditions. The skin feel of thefluorine-containing monomer was significantly improved over that of thecomparison standards.

EXAMPLE 5

Reactants amount (g) Na-neutralized AMPS 50Perfluoroctylethyloxyglyceryl methacrylate 45 t-Butanol 300Trimethylolpropane triacrylate (TMPTA) 1.8 ABAH 1 Poly[N-vinylformamide]8

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of azobisamidopropylhydrochloride (ABAH). The polymer was isolated by removal of the solventunder suction and by subsequent vacuum drying.

What is claimed is:
 1. A water-soluble or water-swellable copolymerobtained by free-radical copolymerization of A) acryloyldimethyltaurineand/or acryloyldimethyltaurates, B) optionally, one or more otherolefinically unsaturated, optionally crosslinking, comonomers containingat least one oxygen, nitrogen, sulfur or phosphorus atom and possessinga molecular weight of less than 500 g/mol, and C) one or more at leastmonofunctional, fluorine-containing components capable of free-radicalpolymerization, at least one fluorine-containing component being acompound of the formula (I) R¹—Y—C_(r)H_(2r)C_(s)F_(2S)CF₃  (I)  whereR¹ is an acryloyl or methacryloyl radical; Y is a chemical bridge, and rand s are stoichiometric coefficients which independently of one anothercan be numbers between 0 and 200, and with the copolymerization takingplace D) optionally in the presence or absence of at least one polymericadditive having number-average molecular weight of from 200 g/mol to 10⁹g/mol.
 2. The water-soluble or water-swellable copolymer of claim 1,wherein the fluorine-containing component C) is selected from the groupconsisting of perfluorohexylethanol methacrylate,perfluorohexoylpropanol methacrylate perfluoroctylethanol methacrylate,perfluoroctylpropanol methacrylate, perfluorohexylethanolyl polyglycolether methacrylate, perfluorohexoylpropanolylpoly[ethylglycol-co-propylene glycol ether] acrylate,perfluoroctylethanolyl poly[ethylglycol-block-co-propylene glycol ether]methacrylate, perfluoroctylpropanolyl polypropylene glycol ethermethacrylate, and mixtures thereof.
 3. The water-soluble orwater-swellable copolymer of claim 1, further comprising one or morecomonomer B).
 4. The water-soluble or water-swellable copolymer asclaimed in claim 3, wherein the comonomer B) is selected from the groupconsisting of unsaturated carboxylic acids, salts of unsaturatedcarboxylic acids, anhydrides of unsaturated carboxylic acids, esters ofunsaturated carboxylic acids with aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic alcohols having 1 to 22 carbon atoms,open-chain N-vinyl amides, cyclic N-vinyl amides having a ring size offrom 3 to 9, amides of acrylic acid, amides of methacrylic acid, amidesof substituted acrylic acids, amides of substituted methacrylic acids,2-vinylpyridine, 4-vinylpyridine, vinyl acetate; styrene, acrylonitrile,vinyl chloride, vinylidene chloride, tetrafluoroethylene,vinylphosphonic acid or the esters or salts thereof, vinylsulfonic acidor the esters or salts thereof, allylphosphonic acid or the esters orsalts thereof, or methallylsulfonic acid or the esters or salts thereof,and mixtures thereof.
 5. The water-soluble or water-swellable copolymerof claim 1, wherein the copolymerization takes place in the presence ofat least one polymeric additive D).
 6. The water-soluble orwater-swellable copolymer as claimed in claim 5, wherein the polymericadditive D) is selected from the group consisting of polyalkyleneglycol, alkylpolyglycol and mixtures thereof or a homopolymer orcopolymer of a compound selected from the group consisting ofN-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide,propylene oxide, acryloyldimethyltaurine, N-vinylcaprolactam,N-vinylmethylacetamide, acrylamide, acrylic acid, methacrylic acid,N-vinylmorpholide, hydroxymethyl methacrylate, diallyldimethylammoniumchloride (DADMAC) and/or [2-(methacryloyloxy)ethyl]trimethylammoniumchloride (MAPTAC), and mixtures thereof.
 7. The water-soluble orwater-swellable copolymer as claimed in claim 6, wherein the polymericadditive D) is selected from the group consisting ofpoly(N-vinylformamides), poly(N-vinylcaprolactams), and copolymers of acompound selected from the group consisting of N-vinylpyrrolidone,N-vinylformamide, acrylic acid, and mixtures thereof.
 8. Thewater-soluble or water-swellable copolymer of claim 1, wherein thecopolymer is crosslinked.
 9. The water-soluble or water-swellablecopolymer of claim 1, wherein the copolymer is prepared by precipitationpolymerization in tert-butanol.
 10. The water-soluble or water-swellablecopolymer of claim 1, wherein the chemical bridge Y is selected from thegroup consisting of —O—, —C(O)—, —C(O)—O—, —S—, —O—CH₂—CH(O—)—CH₂OH,—O—CH₂—CH(OH)—CH₂—O—, —O—SO₂—O—, —O—S(O)—O—, —PH—, —P(CH₃)—, —PO₃—,—NH—, —N(CH₃)—, —O—(C₁-C₅₀)alkyl-O—, —O-phenyl-O—, —O-benzyl-O—,—O—(C₅-C₈)cycloalkyl-O—, —O—(C₁-C₅₀)alkenyl-O—, —O—(CH(CH₃)—CH₂—O)_(n)—,—O—(CH₂—CH₂—O)_(n)—, —O—([CH—CH₂—O]_(n)—[CH₂—CH₂—O]_(m))_(o)—, andmixtures thereof, where n, m, and o independently of one another denotenumbers from 0 to
 200. 11. A water-soluble or water-swellable copolymerobtained by free-radical copolymerization of acryloyldimethyltaurineand/or acryloyldimethyltaurate, with one or more at leastmonofunctional, fluorine-containing component capable of free-radicalpolymerization, at least one fluorine-containing component being acompound of the formula (I) R¹—Y—C_(r)H_(2r)C_(s)F_(2S)CF₃  (I) whereinR¹ is an acryloyl or methacryloyl radical; Y is a radical selected fromthe group consisting of —O—, —C(O)—, —C(O)—O—, —S—, —O—CH₂—CH(O—)—CH₂OH,—O—CH₂—CH(OH)—CH₂—O—, —O—SO₂—O—, —O—S(O)—O—, —PH—, —P(CH₃)—, —PO₃—,—NH—, —N(CH₃)—, —O—(C₁-C₅₀)alkyl-O—, —O-phenyl-O—, —O-benzyl-O—,—O—(C₅-C₈)cycloalkyl-O—, —O—(C₁-C₅₀)alkenyl-O—, —O—(CH(CH₃)—CH₂—O)_(n)—,—O—(CH₂—CH₂—O)_(n)—, —O—([CH—CH₂—O]_(n)—[CH₂—CH₂—O]_(m))_(o)—, andmixtures thereof where n, m, and o independently of one another denotenumbers between 0 and 200, and r and s are stoichiometric coefficientswhich independently of one another can be numbers between 0 and
 200. 12.The water-soluble or water-swellable copolymer of claim 11, saidcopolymerization further comprising being with or in the presence of atleast one of component selected from the group consisting of a) one ormore olefinically unsaturated comonomers containing at least one oxygen,nitrogen, sulfur or phosphorous atom and having a molecular weight ofless than 500 g/mol, b) at least one polymeric additive havingnumber-average molecular weight of from 200 g/mol to 10⁹ g/mol, andmixtures thereof.